CA1304593C - Suspension-type pesticide formulation - Google Patents
Suspension-type pesticide formulationInfo
- Publication number
- CA1304593C CA1304593C CA000542020A CA542020A CA1304593C CA 1304593 C CA1304593 C CA 1304593C CA 000542020 A CA000542020 A CA 000542020A CA 542020 A CA542020 A CA 542020A CA 1304593 C CA1304593 C CA 1304593C
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- CA
- Canada
- Prior art keywords
- agrochemical
- water
- suspension
- type pesticide
- pesticide formulation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
Abstract
ABSTRACT
Highly stable suspension-type pesticide formulations (Flowable) prepared by dispersing fine particles of a hydrophobic solid agrochemical in an aqueous medium, wherein the dispersion is achieved with a surfactant and a water-immisible solvent in which said agrochemical is highly soluble. Even agrochemicals having a melting point lower than 100°C can be formulated into said stable flowables.
Highly stable suspension-type pesticide formulations (Flowable) prepared by dispersing fine particles of a hydrophobic solid agrochemical in an aqueous medium, wherein the dispersion is achieved with a surfactant and a water-immisible solvent in which said agrochemical is highly soluble. Even agrochemicals having a melting point lower than 100°C can be formulated into said stable flowables.
Description
130~5~3 NOVEL SUSPENSION-TYPE PESTICIDE FORMULATION
BACKGROUND OF THE INVENTION
Field of Invention The present invention relates to novel suspension-type pesticite formulations. More particularly, it relates to stable suspension-type pesticide formulations prepared by dispersing fine particles of a hydrophobic solid chemical for agricultural use in water or in an aqueous medium with using a water-immisible solvent in which said chemical is soluble at a high rate (hereinsfter sometimes referred to as water-immisible solvent) ant with a surfactant.
Prior Arts In preparing suspension-type pesticide formulstions by prior arts, it has been usual that hytrophobic solid agrochemicals are milled into fine particles by a try- or wet-grinder and then tispersed in water or in an aqueous solvent in the presence of a qurfactant together with thickning agents (JPN Patent Publication No. 46-20519 and JPN Unexamined Patent Application No. 49-133531).
These prior arts are very useful in the long-term tispersion of a solit sgrochemical which has a relatively high melting point (higher than lO~C) and is very slightly soluble in water (below 50ppm at 20 C) but not convenient for that which has a elting point lower than lOO C (hereinafter sometimes referred to as agroc~emical of lower melting point).
It is believed that crystal growth or aggregation is caused by continual reciprocal collision of the fine particles due to the Van ter Waal's forces. If the fine particles are once aggregated, they are sedimented like clay, then the dispersion of the .... . .. .
` ~L;~ 3 aggregates becomes very hard.
On the other hand, it has been believed that it is helpless to use a solvent as stabilizer in which said agrochemical is highly soluble in preparing suspension-type pesticide formulations, because using such a solvent accelerates crystal growth of said agrochemical. Therefore, as shown in the present invention, it is quite incredible and unexpectable that using a solvent in which said agrochemical is soluble can prevent said agrochemical from aggregation or crystal growth. In any prior arts, no one has succeedet in dispersing the agrochemical of a lower melting point stably over a long period of time.
SUMMARY OF INVENTION
The present invention provites stable suspension-type pesticide formulations preparet by dispersing fine particles of a hydrophobic solit agrochemical in an aqueous medium, wherein the tispersion is achieved with a surfactant ant a water-immisible solvent in which sait agrochemical is highly soluble. The present invention can be appliet to any solit agrochemicals which are very slightly soluble in water (hereinafter referret to as very slightly soluble agrochemical) ant can also be appliet even to solit agrochemicals of lower melting points.
DESCRIPTION OF TNE PREFERRED EMBODIMENT
Problem to be Resolved In the prior arts, when an agrochemical having a lower melting point is disperset, the aggregation, coagulation, fusion, or crystal growth is observed during the storage for long period and accompanied by precipitation of the solid. The resulting precipitates not only get spray-nozzles clogged but al~o get the agrochemical spread unevenly to the plants. The uneven spreat of ,, .,-".,.,, . ~ .
-~3~ 3 the agrochemical causes chemical injury or decrease in the efficacy.
The present inventors have studied and completed the formulstions which have no such defects as mentioned above and can be used as easily as other emulsifiable concentrates or oil solutions can. The present invention can be applied to all the very slightly soluble agrochemicsls and csn also be spplied to solid agrochemicsls hsving melting points higher thsn lOO'C
~hereinsfter referred to as sgrochemicsl of high melting point).
Mesns to Resolve the Problem The stsble squeous suspension-type pesticide formulstions of the present invention msy be prepsred either by sdding ssid wster-immisible solvent to a suspension of the milled hydrophobic solid agrochemicsl dispersed in wster or an squeous medium together with 8 surfactsnt to give hydrophilicity to the sgrochemicsl or by milling the sgrochemicsl into hydrophilic fine psrticles ~fter the addition of said wster-immisible solvent. The method can be exemplified by thst said hydrophobic solit sgrochemic~l is dispersed in water contsining 8 surfsctsnt, millet into fine psrticles by a homogenizer or wet-grinter, snd then 8 water-immisible solvent is sddet thereto. It hss been observet that the hytrophilic fine psrticles in thus prepared concentrstes consist of a solid phsse, liquid phsse, snd sn intermediste phsse thereof.
These phsses sre convertible by the temperature: the crystal growth is preventet by the convertibility.
In the present invention, hydrophobic solid agrochemicsls mean those which are very slightly soluble (lower than 5X
solubility at 20 to 25-C) or practicslly insoluble in water, which may have lower melting point or higher melting point (30-C to ~3C~S~;3 250C). Typical agrochemicals are exemplified below together with their melting points and solubilities (at 20 to 25C in wster):
the herbicides such as 2-methylthio-4-ethylamino-6-isopropylamino-S-triazine (mp 84-85C, 185ppm), 2-chloro-2,6-tiethyl-N-(methoxy-methyl)acetanilide (mp 40-41C, 240ppm), 1-( a . a -dimethylbenzyl)-3-methylphenylurea (mp 73C. 277ppm), 3-(3,4-dichlorophenyl)-1-methoxy-l-methylurea (mp 90-94C, 75ppm), 3-(3,4-dichlorophenyl)-l,l-dimethylurea (mp 158-159C, 18ppm), 2,6-dichlorobenzonitrile (mp 145-l46oc~ 42ppm), 3,5-diiodo-4-octanoyloxybenzonitrile (mp 59-60-C, insoluble), a . a . a -trifluoro-2,6-dinitro-N,N-dipropyl-para-toluidine (mp 45-48-C, insoluble), N-butyl-N-ethyl-a I a . a -trifluoro-2,6-dinitro-N,N-dipropyl-para-toluidine (mp 45-48-C, insoluble), N-butyl-N-ethyl- a, a . a -trifluoro-2,6-dinitro-pars-toluidine (mp 64-65-C, insoluble), and 3-(5-t-butyl-3-isoxazolyl)-l,l-dimethylurea (mp 106-115-C, 300ppm); fungicides such as diisopropyl-1,3-tithiolan-2-ylidene malonate (mp 50-54-5 C.
48ppm), and tetr~chloroisophthalonitrile (mp 25o-25l-c~ 0.6ppm);
and insecticides such as dimethylethylsulfinyl isopropylthio-phosphate (mp 36-C, insoluble), m-tolyl-N-methylcarbamate (mp 74-75-C, 0.26%), 3-diethoxyphoqphorylthiomethyl-6-chlorobenzoxazolone (mp 48 C, lOppm), and methyl isothiocyanate (mp 35-36-C, 0.76%).
In milling hydrophobic solid agrochemicals into fine particles, a mixer or homogenizer, and if necessary, colloid mill, attrition mill, sand grinder, or the like may be employed. The average size of the hydrophilic fine particles may be smaller than about 20~ m, more preferably smaller than about 5~ m, and most preferably smaller than about 1~ m.
The water-immisible solvents in which the hydrophobic agrochemical is highly soluble include hy *ocarbons such a~
... . . . .
13~ 3 cyclohexane, benzene, toluene, xylene, ethylbenzene and the like;
halogenated hydrocsrbons such as dichloromethane, chloroform, carbon tetrachloride, chlorobenzene, and the like; C~-CI2 alkyl alcohols such as n-hexyl alcohol, n-octyl alcohol, n-tecyl alcohol, and the like; ethers such as propyl ether, n-butyl ether, methyl phenyl ether, ethyl phenyl ether and the like; ketones such as acetophenone, cyclophenone, cyclohexanone, isophorone, and the like; esters such as methyl acetate, ethyl acetate, methyl benzoate, ethyl benzoate, snd the like; fatty acids such as oleic acid and the like; and aromatic hydrocarbons having a nitrogen atom such as nitrobenzene, aniline, and the like: from the listed solvents, one in which the agrochemical employed is highly soluble may be chosen.
The relative amount of a water-immisible solvent to that of hydrophobic solit agrochemical may not be limitted because it varies with the combination, especially with the solubility of the agrochemical in the solvent. Among others-, it should be noted that the solvent must be used in a smaller amount thPn necessary amount to tissolve the agrochemical completely. Further, the amount of the solvent to be used varies with kints of surfactants or other adtitiveQ or t_e amount of them. Generally speaking, the solvents may be employed at a rate of 20 to 200~, more preferably of 30 to 120~ by weight, to the hydrophobic solid agrochemicals uset.
Aggregation or crystal growth is often observed if the solvent is used in a smaller amount than the foregoing lowest limitation, and on the other hand, if it is used in 8 larger amount than the highest limitation, fusion is accelerated ant, consequently, phase separation is sometimes observet in the concentrates.
The water-immisible solvents may be adtet before or after the _5_ ~3~
milling of the hydrophobic solid agrochemicals. Optimum prescription may be designed according to the kinds of the agrochemicals and other additives or the concentrations thereof and to the requested qualities of the formulations.
Surfactants used in this invention may be anionic, cstionic, nonionic, or amphoteric one. Practically, surfactants used as agricultural auxiliaries may be used for this purpose. For exsmple, snionic surfactsnts include fstty acid sslts or esters such as alkylnaphthalenesulfonste, dotecylbenzenesulfonste, dislkylsulfosuccinste, magnesium stearate, snt the like, polyoxy-ethylene phenylphenolphosphate, polyoxyethylene phenylphenol-sulfste, polyoxyethylene phenylphenolsulfonste, nsphtslenesulfo-nste formsldehyte condensste, ligninsulfonste, polyoxyslkylene block polymer sulfste, snt the like Nonionic surfactants inclute polyoxyslkylene alkyl ether, polyoxyethylenesorbitsn~lkylste, sorbitanslkylste, polyoxyethylenestyrenatet phenyl ether, polyoxyethylene fatty acit ether, polyoxyethylene fstty scid ester, polyoxyslkylene block polymer, and the like.
Surfsctsnts msy be usually employed st a r~te of 0.1 to 20 %
by weight to the final formulstion, more preferably at 0.5 to 10 %, most preferably at 1 to 5 %.
If desired, polymers such as carboxymethyl cellulose, polyvinyl slcohol, polyacrylic scid or the sslt thereof, slginic acid salt, polyvinyl pyrrolidone, gum arsbic, xanthan gm, gelatin, and the like; and inorganic materials such ss white carbon, talc, bentonite, clay, snd the like may be employed ss thickning agents to prevent said particles from sggregation or precipitation. Further, known depressers of freezing point or suspensibility-potencisting agents including diols such ss ... . .
J~3C~5~3 ethylene glycol, propylene glycol, or the like; triols such ~s glycerol or the like; inorganic salts such as sulfate, carbonate, phosphate, or the like; urea; and polyacrylic acid oligomer may be employed in this invention.
In order to increase st~bility of agrochemicals, if desired, the formulation may be ~djusted to a preferable pH value with inorgsnic or organic acids or bases. For example, sodium hydroxide, potassium, sodium phosphate, mono-, di-, or tri-ethanolsmine, and hydrochloric acid may be prefer~bly employed.
The present invention not only has teveloped a method for stabilization of the suspension-type pesticide formulations, but also made it possible to formulate the practically water-insoluble sgrochemicals having melting points lower than 100-C, which have been hard to be formulated into suspension with water or with an aqueous solvent.
The present invention has realized the increase of efficacy and decrease of chemical injury in field use. Additionally, it provides other various advsntages in practical aspects: for ex~mple, (1) low costs in preparing formulation because water can be uset in pl~ce of both inorganic carriers and organic solvents which must be used as extending agents in preparing wett~ble powters or emulsifiable concentrates, (2) safe operability in spraying the chemicals, and (3) prevention of environment pollution.
The present invention is explained by the following examples and experiments in more detail, which are not intended to limit the scope of the invention.
., .
~3~ 3 Into 435g of 2.0% aqueous solution (70C) of polyoxyethylene-phenylphenolphosphate was dissolved 65g of 3,5-diiodo-4-octanoyl-oxybenzonitrile and the mixture WAS then cooled down to 25C while being stirred with a T.K. sutohomogenizer type Mm (made by Toku-shu Kika Co., Ltd.). The mixture was millet for 10 minutes by a wetting method using a Dinomill type KDL (made by Willy A.
Bachofen AG Maschinefabrik) to give an aqueous suspension.
To 300g of the aqueous suspension were added 30g of dichloro-methane, 4.4g of polyacrylic acid, 12.0g of polyacrylic acid oligomer, 44g of propylene glycol, and then a necessary amount of ion exchange water to make the whole 600g. Thus prepared suspension concentrate contains at 6X the active ingretient.
To 300g of the aqueous suspension prepared in Example 1 were addet 30g of acetophenone, 4.4g of polyacrylic acid, 12.0g of polyacrylic acid oligomer, 60g of propylene glycol, and then a necessary smount of ion exchange water to make the whole 600g.
Thus prepared suspension concentrate contains at 6X the sctive ingredient.
To 300g of the aqueous suspension prepsret in Example 1 were addet 30g of isophorone, 4.4g of polyacrylic acid, 12.0g of polyacrylic acid oligomer, 48g of propylene glycol, ant then a necessary amount of ion exchange water to make the whole 600g.
Thus preparet suspension concentrate contains at 6X the active ingretient.
To 300g of the aqueous suspension prepared in Example 1 were i. .
13U~5~3 added 30g of n-octyl alcohol, 4.4g of polyacrylic acit, 12.0g of polyacrylic acid oligomer, 75g of propylene glycol, and then a necessary amount of ion exchsnge water to make the whole 600g.
Thus prepared suspension concentrate contains at 6% the active ingredient.
In 346g of 3.5X aqueous solution (70-C) of polyoxyethylene-phenylphenolphosphate was dissolved 154g of a . a . a -trifluoro-2, 6-dinitro-N,N-dipropyl-p~ra-toluidine snd the mixture was then cocled down to 25C while being stirred with a T.K.autohomogenizer type Mm (made by Tokushu Kika Co., Ltd.). The mixture was milled for 15 minutes by a wetting method using a Dinomill type KDL (made by Willy A. Bachofen AG Maschinefabrik) to give an aqueous suspension.
To 300g of the aqueous suspension were addet 84g of dichloro-methane, 2.0g of polyacrylic acid, 33g of ethylene glycol, and then a necessary amount of ion exchsnge water to make the whole 450g. Thus prepared suspension concentrste contains at 20% the sctive ingredient.
In 381g of 1.4X aqueous solution (70-C) of polyoxyethylene-polyarylalkyl ether was dis~ol~ed ll9g of N-butyl-N-ethyl-a , a .
a -trifluoro-2,6-dinitroparatoluitine ant the mixture was then cooled down to 25-C while being stirred with a T.K.autohomogenizer type Mm (made by Tokushu Kika Co., Ltd.). The mixture WQS
milled for 15 minutes by a wetting method using a Dinomill type KDL (made.by Willy A. Bachofen AG Maschinefabrik) to give an aqueous suspension.
To 300g of the aqueous suspension were added 84g of _g_ ,, .. . - .
, .
13~ 3 isophorone, 2.0g of polyacrylic acid, 30g of ethylene glycol, and then a necessary smount of ion exchange water to make the whole 450g. Thus prepared suspension concentrate contains at 15X the active ingred1ent.
In 346g of 3.5~ aqueous solution (70~C) of polyoxyethylene-phenylphenolphosphate was dissolved 154g of 3-diethoxyphosphor-ylthiomethyl-6-chlorobenzoxazorone and the mixture was then cooled down to 25-C while being stirred with a T.K. autohomogenizer type Mm (made by Tokushu Kika Co., Ltd.). The mixture WBS milled for 15 minutes by a wetting method using a Dinomill type KDL (made by Willy A. Bachofen AG Maschinefabrik) to give an aqueous suspension.
To 300g of the aqueous suspension were adted 63g of dichloro-methane, 2.0g of polyacrylic acid, 30g of ethylene glycol, and then a necessary amount of ion exchange water to make the whole 450g. Thus preparet suspension concentrate contains at 20% the active ingredient.
In 346g of 3,5X aqueous solution (70-C) of polyoxyethylene-phenylphenolphosphate was tissolvet 154g of 3-diethoxyphosphor-ylthiomethyl-6-chlorobenzoxazorone ant the mixture was then coolet town to 25-C while being stirret with a T.K. autohomogenizer type Mm (made by Tokushu Kika Co., Ltd.). The mixture was milled for 15 minutes by a wetting methot using a Dinomill type KDL (mate by Willy A. B~chofen AG Maschinefabrik) to give an aqueous suspension.
To 300g of the aqueous suspension were atded 63g of benzene, 2.0g of polyacrylic acit, 30g of ethylene glycol, and then a ~3~5~3 necessary amount of ion exchange wster to make the whole 450g.
Thus prepared suspension concentrate contains at 20% the active ingredient.
In 200g of 7.5% aqueous solution (50c) of polyoxyethylene-phenylphenolphosphate was dissolved 165g of methyl isothiocyanate.
Toluene (60g), 1.3g of polyacrylic acid, 7.5g of polyacrylic acid oligomer, and 35g of ethylene glycol were sdded to the mixture and finally a necessary amount of ion exchange water to mske the whole 500g was added thereto. The resulting mixture was cooled down to 25-C while being stirret with a T.K. autohomogenizer type Mm (made by Tokushu Kika Co., Ltd.) to give a suspension concentrate which contains the active ingredient at 30X.
In 200g of 7 5X aqueous solution (50 C) of polyoxyethylene-phenylphenolphosphate was dissolved 165g of methyl isothiocyanate.
Dichloromethane (70g), 2.3g of polyacrylic acit, 75g of polyacry-lic acit oligomer, 30g of ethylene glycol, and then a necessary amount of ion exchange water to make the whole 500g were added to the mixture. The resulting mixture was cooled down to 25-C while being stirred with a T.K. autohomogenizer type Mm (msde by Toku-shu Kiks Co., Ltd.) to give a suspension concentrate which contains the active ingredient at 30%.
In 200g of 7 5X aqueous solution (50-C) of polyoxyethylene-phenylphenolphosphate was dissolved 165g of methyl isothiocyanste.
Yylene (65g), 2.0g of polyacrylic acid, lOg of polyacrylic acid oligomer, 40g of ethylene glycol, and then a necessary amount of ion exchange water to make the whole 500g were added to the 13~45~3 mixture. The resulting mixture was cooled down to 25C while being stirred with a T.K. autohomogenizer type Mm (made by Tokushu Kika Co., Ltd.) to give a suspension concentrate which contains the active ingredient at 30%.
In 150g of 10.0% aqueous solution (50C) of polyoxyethylene-phenylphenolphosphate was dissolved 220g of methyl isothiocyanate.
Cyclohexanone (75g), 2.0g of polyacrylic acid, 15g of polyacrylic acid oligomer, 25g of ethylene glycol, snd then a necessary smount of ion exchange water to make the whole 500g were added to the mixture. The resulting mixture was cooled down to 25'C while being stirred with a T.K. autohomogenizer type Mm (made by Tokushu Kika Co., Ltd.) to give a suspension concentrate which contains the active ingredient at 40%.
For the comparison with the formulations of the present invention, suspension concentrates of prior arts were prepared in the following Reference Examples.
To 300g of the aqueous suspension preparet in Ex~mple 1 were sdded 5.0g of polyacrylic acid, 12.0g of polyscrylic ~cid oligomer, 72g of propylene glycol, and then a necessary amount of ion exchsnge w~ter to make the whole 600g. Thus prepared suspension concentrate contains at 6% the active ingredient.
To 300g of the aqueous suspension prepared in Exsmple 1 were added 2.0g of polyacrylic acid, 40g of ethylene glycol, and then a necessary amount of ion exchange water to make the whole 450g.
Thus prep~red suspension concentrate contains at 15% the active ingredient.
` :13~4~3 Experiment The novel suspension type pesticide formulations prepared in the Examples above were tested on the physical properties of them and stabilities at 40C for one month, according to the method shown below.
(Test Method for Physical Properties) (1) Mean particle size:
Suspension-type pesticide formulations each was diluted with distilled water up to 1/3000 to 1/1000 concentration. The particle size was measured by a micron photosizer (Micron Photosizer SK-2000SR: made by Seishin Enterprise Co., Ltd.).
(2) Suspensability:
Weighed l.Og (2.5g as to formulations in Examples 9-12) of a suspension-type pesticide formulation was diluted with hsrd water (20-C, hardness 3) to make the whole 250 ml, by using which suspensibili~y was measured according to the Official Testing Methods for Physical Properties of Agricultural Chemic~ls (Agri-cultural Chemicals Inspection Center, Ministry of Agriculture, Forestry & Fishery).
BACKGROUND OF THE INVENTION
Field of Invention The present invention relates to novel suspension-type pesticite formulations. More particularly, it relates to stable suspension-type pesticide formulations prepared by dispersing fine particles of a hydrophobic solid chemical for agricultural use in water or in an aqueous medium with using a water-immisible solvent in which said chemical is soluble at a high rate (hereinsfter sometimes referred to as water-immisible solvent) ant with a surfactant.
Prior Arts In preparing suspension-type pesticide formulstions by prior arts, it has been usual that hytrophobic solid agrochemicals are milled into fine particles by a try- or wet-grinder and then tispersed in water or in an aqueous solvent in the presence of a qurfactant together with thickning agents (JPN Patent Publication No. 46-20519 and JPN Unexamined Patent Application No. 49-133531).
These prior arts are very useful in the long-term tispersion of a solit sgrochemical which has a relatively high melting point (higher than lO~C) and is very slightly soluble in water (below 50ppm at 20 C) but not convenient for that which has a elting point lower than lOO C (hereinafter sometimes referred to as agroc~emical of lower melting point).
It is believed that crystal growth or aggregation is caused by continual reciprocal collision of the fine particles due to the Van ter Waal's forces. If the fine particles are once aggregated, they are sedimented like clay, then the dispersion of the .... . .. .
` ~L;~ 3 aggregates becomes very hard.
On the other hand, it has been believed that it is helpless to use a solvent as stabilizer in which said agrochemical is highly soluble in preparing suspension-type pesticide formulations, because using such a solvent accelerates crystal growth of said agrochemical. Therefore, as shown in the present invention, it is quite incredible and unexpectable that using a solvent in which said agrochemical is soluble can prevent said agrochemical from aggregation or crystal growth. In any prior arts, no one has succeedet in dispersing the agrochemical of a lower melting point stably over a long period of time.
SUMMARY OF INVENTION
The present invention provites stable suspension-type pesticide formulations preparet by dispersing fine particles of a hydrophobic solit agrochemical in an aqueous medium, wherein the tispersion is achieved with a surfactant ant a water-immisible solvent in which sait agrochemical is highly soluble. The present invention can be appliet to any solit agrochemicals which are very slightly soluble in water (hereinafter referret to as very slightly soluble agrochemical) ant can also be appliet even to solit agrochemicals of lower melting points.
DESCRIPTION OF TNE PREFERRED EMBODIMENT
Problem to be Resolved In the prior arts, when an agrochemical having a lower melting point is disperset, the aggregation, coagulation, fusion, or crystal growth is observed during the storage for long period and accompanied by precipitation of the solid. The resulting precipitates not only get spray-nozzles clogged but al~o get the agrochemical spread unevenly to the plants. The uneven spreat of ,, .,-".,.,, . ~ .
-~3~ 3 the agrochemical causes chemical injury or decrease in the efficacy.
The present inventors have studied and completed the formulstions which have no such defects as mentioned above and can be used as easily as other emulsifiable concentrates or oil solutions can. The present invention can be applied to all the very slightly soluble agrochemicsls and csn also be spplied to solid agrochemicsls hsving melting points higher thsn lOO'C
~hereinsfter referred to as sgrochemicsl of high melting point).
Mesns to Resolve the Problem The stsble squeous suspension-type pesticide formulstions of the present invention msy be prepsred either by sdding ssid wster-immisible solvent to a suspension of the milled hydrophobic solid agrochemicsl dispersed in wster or an squeous medium together with 8 surfactsnt to give hydrophilicity to the sgrochemicsl or by milling the sgrochemicsl into hydrophilic fine psrticles ~fter the addition of said wster-immisible solvent. The method can be exemplified by thst said hydrophobic solit sgrochemic~l is dispersed in water contsining 8 surfsctsnt, millet into fine psrticles by a homogenizer or wet-grinter, snd then 8 water-immisible solvent is sddet thereto. It hss been observet that the hytrophilic fine psrticles in thus prepared concentrstes consist of a solid phsse, liquid phsse, snd sn intermediste phsse thereof.
These phsses sre convertible by the temperature: the crystal growth is preventet by the convertibility.
In the present invention, hydrophobic solid agrochemicsls mean those which are very slightly soluble (lower than 5X
solubility at 20 to 25-C) or practicslly insoluble in water, which may have lower melting point or higher melting point (30-C to ~3C~S~;3 250C). Typical agrochemicals are exemplified below together with their melting points and solubilities (at 20 to 25C in wster):
the herbicides such as 2-methylthio-4-ethylamino-6-isopropylamino-S-triazine (mp 84-85C, 185ppm), 2-chloro-2,6-tiethyl-N-(methoxy-methyl)acetanilide (mp 40-41C, 240ppm), 1-( a . a -dimethylbenzyl)-3-methylphenylurea (mp 73C. 277ppm), 3-(3,4-dichlorophenyl)-1-methoxy-l-methylurea (mp 90-94C, 75ppm), 3-(3,4-dichlorophenyl)-l,l-dimethylurea (mp 158-159C, 18ppm), 2,6-dichlorobenzonitrile (mp 145-l46oc~ 42ppm), 3,5-diiodo-4-octanoyloxybenzonitrile (mp 59-60-C, insoluble), a . a . a -trifluoro-2,6-dinitro-N,N-dipropyl-para-toluidine (mp 45-48-C, insoluble), N-butyl-N-ethyl-a I a . a -trifluoro-2,6-dinitro-N,N-dipropyl-para-toluidine (mp 45-48-C, insoluble), N-butyl-N-ethyl- a, a . a -trifluoro-2,6-dinitro-pars-toluidine (mp 64-65-C, insoluble), and 3-(5-t-butyl-3-isoxazolyl)-l,l-dimethylurea (mp 106-115-C, 300ppm); fungicides such as diisopropyl-1,3-tithiolan-2-ylidene malonate (mp 50-54-5 C.
48ppm), and tetr~chloroisophthalonitrile (mp 25o-25l-c~ 0.6ppm);
and insecticides such as dimethylethylsulfinyl isopropylthio-phosphate (mp 36-C, insoluble), m-tolyl-N-methylcarbamate (mp 74-75-C, 0.26%), 3-diethoxyphoqphorylthiomethyl-6-chlorobenzoxazolone (mp 48 C, lOppm), and methyl isothiocyanate (mp 35-36-C, 0.76%).
In milling hydrophobic solid agrochemicals into fine particles, a mixer or homogenizer, and if necessary, colloid mill, attrition mill, sand grinder, or the like may be employed. The average size of the hydrophilic fine particles may be smaller than about 20~ m, more preferably smaller than about 5~ m, and most preferably smaller than about 1~ m.
The water-immisible solvents in which the hydrophobic agrochemical is highly soluble include hy *ocarbons such a~
... . . . .
13~ 3 cyclohexane, benzene, toluene, xylene, ethylbenzene and the like;
halogenated hydrocsrbons such as dichloromethane, chloroform, carbon tetrachloride, chlorobenzene, and the like; C~-CI2 alkyl alcohols such as n-hexyl alcohol, n-octyl alcohol, n-tecyl alcohol, and the like; ethers such as propyl ether, n-butyl ether, methyl phenyl ether, ethyl phenyl ether and the like; ketones such as acetophenone, cyclophenone, cyclohexanone, isophorone, and the like; esters such as methyl acetate, ethyl acetate, methyl benzoate, ethyl benzoate, snd the like; fatty acids such as oleic acid and the like; and aromatic hydrocarbons having a nitrogen atom such as nitrobenzene, aniline, and the like: from the listed solvents, one in which the agrochemical employed is highly soluble may be chosen.
The relative amount of a water-immisible solvent to that of hydrophobic solit agrochemical may not be limitted because it varies with the combination, especially with the solubility of the agrochemical in the solvent. Among others-, it should be noted that the solvent must be used in a smaller amount thPn necessary amount to tissolve the agrochemical completely. Further, the amount of the solvent to be used varies with kints of surfactants or other adtitiveQ or t_e amount of them. Generally speaking, the solvents may be employed at a rate of 20 to 200~, more preferably of 30 to 120~ by weight, to the hydrophobic solid agrochemicals uset.
Aggregation or crystal growth is often observed if the solvent is used in a smaller amount than the foregoing lowest limitation, and on the other hand, if it is used in 8 larger amount than the highest limitation, fusion is accelerated ant, consequently, phase separation is sometimes observet in the concentrates.
The water-immisible solvents may be adtet before or after the _5_ ~3~
milling of the hydrophobic solid agrochemicals. Optimum prescription may be designed according to the kinds of the agrochemicals and other additives or the concentrations thereof and to the requested qualities of the formulations.
Surfactants used in this invention may be anionic, cstionic, nonionic, or amphoteric one. Practically, surfactants used as agricultural auxiliaries may be used for this purpose. For exsmple, snionic surfactsnts include fstty acid sslts or esters such as alkylnaphthalenesulfonste, dotecylbenzenesulfonste, dislkylsulfosuccinste, magnesium stearate, snt the like, polyoxy-ethylene phenylphenolphosphate, polyoxyethylene phenylphenol-sulfste, polyoxyethylene phenylphenolsulfonste, nsphtslenesulfo-nste formsldehyte condensste, ligninsulfonste, polyoxyslkylene block polymer sulfste, snt the like Nonionic surfactants inclute polyoxyslkylene alkyl ether, polyoxyethylenesorbitsn~lkylste, sorbitanslkylste, polyoxyethylenestyrenatet phenyl ether, polyoxyethylene fatty acit ether, polyoxyethylene fstty scid ester, polyoxyslkylene block polymer, and the like.
Surfsctsnts msy be usually employed st a r~te of 0.1 to 20 %
by weight to the final formulstion, more preferably at 0.5 to 10 %, most preferably at 1 to 5 %.
If desired, polymers such as carboxymethyl cellulose, polyvinyl slcohol, polyacrylic scid or the sslt thereof, slginic acid salt, polyvinyl pyrrolidone, gum arsbic, xanthan gm, gelatin, and the like; and inorganic materials such ss white carbon, talc, bentonite, clay, snd the like may be employed ss thickning agents to prevent said particles from sggregation or precipitation. Further, known depressers of freezing point or suspensibility-potencisting agents including diols such ss ... . .
J~3C~5~3 ethylene glycol, propylene glycol, or the like; triols such ~s glycerol or the like; inorganic salts such as sulfate, carbonate, phosphate, or the like; urea; and polyacrylic acid oligomer may be employed in this invention.
In order to increase st~bility of agrochemicals, if desired, the formulation may be ~djusted to a preferable pH value with inorgsnic or organic acids or bases. For example, sodium hydroxide, potassium, sodium phosphate, mono-, di-, or tri-ethanolsmine, and hydrochloric acid may be prefer~bly employed.
The present invention not only has teveloped a method for stabilization of the suspension-type pesticide formulations, but also made it possible to formulate the practically water-insoluble sgrochemicals having melting points lower than 100-C, which have been hard to be formulated into suspension with water or with an aqueous solvent.
The present invention has realized the increase of efficacy and decrease of chemical injury in field use. Additionally, it provides other various advsntages in practical aspects: for ex~mple, (1) low costs in preparing formulation because water can be uset in pl~ce of both inorganic carriers and organic solvents which must be used as extending agents in preparing wett~ble powters or emulsifiable concentrates, (2) safe operability in spraying the chemicals, and (3) prevention of environment pollution.
The present invention is explained by the following examples and experiments in more detail, which are not intended to limit the scope of the invention.
., .
~3~ 3 Into 435g of 2.0% aqueous solution (70C) of polyoxyethylene-phenylphenolphosphate was dissolved 65g of 3,5-diiodo-4-octanoyl-oxybenzonitrile and the mixture WAS then cooled down to 25C while being stirred with a T.K. sutohomogenizer type Mm (made by Toku-shu Kika Co., Ltd.). The mixture was millet for 10 minutes by a wetting method using a Dinomill type KDL (made by Willy A.
Bachofen AG Maschinefabrik) to give an aqueous suspension.
To 300g of the aqueous suspension were added 30g of dichloro-methane, 4.4g of polyacrylic acid, 12.0g of polyacrylic acid oligomer, 44g of propylene glycol, and then a necessary amount of ion exchange water to make the whole 600g. Thus prepared suspension concentrate contains at 6X the active ingretient.
To 300g of the aqueous suspension prepared in Example 1 were addet 30g of acetophenone, 4.4g of polyacrylic acid, 12.0g of polyacrylic acid oligomer, 60g of propylene glycol, and then a necessary smount of ion exchange water to make the whole 600g.
Thus prepared suspension concentrate contains at 6X the sctive ingredient.
To 300g of the aqueous suspension prepsret in Example 1 were addet 30g of isophorone, 4.4g of polyacrylic acid, 12.0g of polyacrylic acid oligomer, 48g of propylene glycol, ant then a necessary amount of ion exchange water to make the whole 600g.
Thus preparet suspension concentrate contains at 6X the active ingretient.
To 300g of the aqueous suspension prepared in Example 1 were i. .
13U~5~3 added 30g of n-octyl alcohol, 4.4g of polyacrylic acit, 12.0g of polyacrylic acid oligomer, 75g of propylene glycol, and then a necessary amount of ion exchsnge water to make the whole 600g.
Thus prepared suspension concentrate contains at 6% the active ingredient.
In 346g of 3.5X aqueous solution (70-C) of polyoxyethylene-phenylphenolphosphate was dissolved 154g of a . a . a -trifluoro-2, 6-dinitro-N,N-dipropyl-p~ra-toluidine snd the mixture was then cocled down to 25C while being stirred with a T.K.autohomogenizer type Mm (made by Tokushu Kika Co., Ltd.). The mixture was milled for 15 minutes by a wetting method using a Dinomill type KDL (made by Willy A. Bachofen AG Maschinefabrik) to give an aqueous suspension.
To 300g of the aqueous suspension were addet 84g of dichloro-methane, 2.0g of polyacrylic acid, 33g of ethylene glycol, and then a necessary amount of ion exchsnge water to make the whole 450g. Thus prepared suspension concentrste contains at 20% the sctive ingredient.
In 381g of 1.4X aqueous solution (70-C) of polyoxyethylene-polyarylalkyl ether was dis~ol~ed ll9g of N-butyl-N-ethyl-a , a .
a -trifluoro-2,6-dinitroparatoluitine ant the mixture was then cooled down to 25-C while being stirred with a T.K.autohomogenizer type Mm (made by Tokushu Kika Co., Ltd.). The mixture WQS
milled for 15 minutes by a wetting method using a Dinomill type KDL (made.by Willy A. Bachofen AG Maschinefabrik) to give an aqueous suspension.
To 300g of the aqueous suspension were added 84g of _g_ ,, .. . - .
, .
13~ 3 isophorone, 2.0g of polyacrylic acid, 30g of ethylene glycol, and then a necessary smount of ion exchange water to make the whole 450g. Thus prepared suspension concentrate contains at 15X the active ingred1ent.
In 346g of 3.5~ aqueous solution (70~C) of polyoxyethylene-phenylphenolphosphate was dissolved 154g of 3-diethoxyphosphor-ylthiomethyl-6-chlorobenzoxazorone and the mixture was then cooled down to 25-C while being stirred with a T.K. autohomogenizer type Mm (made by Tokushu Kika Co., Ltd.). The mixture WBS milled for 15 minutes by a wetting method using a Dinomill type KDL (made by Willy A. Bachofen AG Maschinefabrik) to give an aqueous suspension.
To 300g of the aqueous suspension were adted 63g of dichloro-methane, 2.0g of polyacrylic acid, 30g of ethylene glycol, and then a necessary amount of ion exchange water to make the whole 450g. Thus preparet suspension concentrate contains at 20% the active ingredient.
In 346g of 3,5X aqueous solution (70-C) of polyoxyethylene-phenylphenolphosphate was tissolvet 154g of 3-diethoxyphosphor-ylthiomethyl-6-chlorobenzoxazorone ant the mixture was then coolet town to 25-C while being stirret with a T.K. autohomogenizer type Mm (made by Tokushu Kika Co., Ltd.). The mixture was milled for 15 minutes by a wetting methot using a Dinomill type KDL (mate by Willy A. B~chofen AG Maschinefabrik) to give an aqueous suspension.
To 300g of the aqueous suspension were atded 63g of benzene, 2.0g of polyacrylic acit, 30g of ethylene glycol, and then a ~3~5~3 necessary amount of ion exchange wster to make the whole 450g.
Thus prepared suspension concentrate contains at 20% the active ingredient.
In 200g of 7.5% aqueous solution (50c) of polyoxyethylene-phenylphenolphosphate was dissolved 165g of methyl isothiocyanate.
Toluene (60g), 1.3g of polyacrylic acid, 7.5g of polyacrylic acid oligomer, and 35g of ethylene glycol were sdded to the mixture and finally a necessary amount of ion exchange water to mske the whole 500g was added thereto. The resulting mixture was cooled down to 25-C while being stirret with a T.K. autohomogenizer type Mm (made by Tokushu Kika Co., Ltd.) to give a suspension concentrate which contains the active ingredient at 30X.
In 200g of 7 5X aqueous solution (50 C) of polyoxyethylene-phenylphenolphosphate was dissolved 165g of methyl isothiocyanate.
Dichloromethane (70g), 2.3g of polyacrylic acit, 75g of polyacry-lic acit oligomer, 30g of ethylene glycol, and then a necessary amount of ion exchange water to make the whole 500g were added to the mixture. The resulting mixture was cooled down to 25-C while being stirred with a T.K. autohomogenizer type Mm (msde by Toku-shu Kiks Co., Ltd.) to give a suspension concentrate which contains the active ingredient at 30%.
In 200g of 7 5X aqueous solution (50-C) of polyoxyethylene-phenylphenolphosphate was dissolved 165g of methyl isothiocyanste.
Yylene (65g), 2.0g of polyacrylic acid, lOg of polyacrylic acid oligomer, 40g of ethylene glycol, and then a necessary amount of ion exchange water to make the whole 500g were added to the 13~45~3 mixture. The resulting mixture was cooled down to 25C while being stirred with a T.K. autohomogenizer type Mm (made by Tokushu Kika Co., Ltd.) to give a suspension concentrate which contains the active ingredient at 30%.
In 150g of 10.0% aqueous solution (50C) of polyoxyethylene-phenylphenolphosphate was dissolved 220g of methyl isothiocyanate.
Cyclohexanone (75g), 2.0g of polyacrylic acid, 15g of polyacrylic acid oligomer, 25g of ethylene glycol, snd then a necessary smount of ion exchange water to make the whole 500g were added to the mixture. The resulting mixture was cooled down to 25'C while being stirred with a T.K. autohomogenizer type Mm (made by Tokushu Kika Co., Ltd.) to give a suspension concentrate which contains the active ingredient at 40%.
For the comparison with the formulations of the present invention, suspension concentrates of prior arts were prepared in the following Reference Examples.
To 300g of the aqueous suspension preparet in Ex~mple 1 were sdded 5.0g of polyacrylic acid, 12.0g of polyscrylic ~cid oligomer, 72g of propylene glycol, and then a necessary amount of ion exchsnge w~ter to make the whole 600g. Thus prepared suspension concentrate contains at 6% the active ingredient.
To 300g of the aqueous suspension prepared in Exsmple 1 were added 2.0g of polyacrylic acid, 40g of ethylene glycol, and then a necessary amount of ion exchange water to make the whole 450g.
Thus prep~red suspension concentrate contains at 15% the active ingredient.
` :13~4~3 Experiment The novel suspension type pesticide formulations prepared in the Examples above were tested on the physical properties of them and stabilities at 40C for one month, according to the method shown below.
(Test Method for Physical Properties) (1) Mean particle size:
Suspension-type pesticide formulations each was diluted with distilled water up to 1/3000 to 1/1000 concentration. The particle size was measured by a micron photosizer (Micron Photosizer SK-2000SR: made by Seishin Enterprise Co., Ltd.).
(2) Suspensability:
Weighed l.Og (2.5g as to formulations in Examples 9-12) of a suspension-type pesticide formulation was diluted with hsrd water (20-C, hardness 3) to make the whole 250 ml, by using which suspensibili~y was measured according to the Official Testing Methods for Physical Properties of Agricultural Chemic~ls (Agri-cultural Chemicals Inspection Center, Ministry of Agriculture, Forestry & Fishery).
(3) Viscosity:
The viscosity of each suspension-type pesticide formulation at 20-C was measured by a capirally viscometer (Top Kinem~tic Viscosimeter: made by Sogorikag~ku Glass Works Co., Ltd.).
i.3~J~5!~3 ~ ~ ___ _ __ _ __ _--o ~ _ ~ 8 8 o ~ _ ~i æ 8 ~ 8 8 8 ~ ~
~ ~.. , _ _ _ c: Q) E E ~ El E I; E 6 El E~
x ~ ~1 ~1 ~ ~ ~1 ::1 ~1 ~1 ~1 ~ ~1 ~ ~d-J, N ~8 ~ O 0 ~O ~!; _I O 8~ O ~
s~ o o o o _, ~ o _, o n ~
V
~ ~ 3 ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ It c c _ ~ Z Z Z ~ Z _ ~ ~ ~ Z ~ Z ~ ~
~o ~ ~ ~ o~ ~ o~ o ~ r~ o~ a~ ~ n ul .~_ ~ R ~ R ~i o~ ~ ~ ~t ~ ~ ~ ~ ~ ~
CJO _ , __ _ _ _ ~2L
I P~ 00 ~ CO O ~ ~ O OD O~ aD O ~ O ~ Ul ~ ~.~ _ æ O O O _ O æ ___ ` æ _ O ~ E E E E Ei E3 E ~ E ~3 E3 ~ ~ 4~
-l ~ ~ ~ u~ `o l~ o~ o` -~ -~ -~ ~ ~ ~
~ ~,~
_ 14 --13~
Conclusion As clearly recognized from the foregoing Experimental dsta, significant aggregation or crystal growth was observed and also suspensibility was decreased to about 50% after one month ~t 40C
on the reference formulations which represent the prior arts;
while on the formulations of tbe present invention, no crystal growth nor decrease in suspensibility was observed under tbe ssme conditions as the reference.
The viscosity of each suspension-type pesticide formulation at 20-C was measured by a capirally viscometer (Top Kinem~tic Viscosimeter: made by Sogorikag~ku Glass Works Co., Ltd.).
i.3~J~5!~3 ~ ~ ___ _ __ _ __ _--o ~ _ ~ 8 8 o ~ _ ~i æ 8 ~ 8 8 8 ~ ~
~ ~.. , _ _ _ c: Q) E E ~ El E I; E 6 El E~
x ~ ~1 ~1 ~ ~ ~1 ::1 ~1 ~1 ~1 ~ ~1 ~ ~d-J, N ~8 ~ O 0 ~O ~!; _I O 8~ O ~
s~ o o o o _, ~ o _, o n ~
V
~ ~ 3 ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ It c c _ ~ Z Z Z ~ Z _ ~ ~ ~ Z ~ Z ~ ~
~o ~ ~ ~ o~ ~ o~ o ~ r~ o~ a~ ~ n ul .~_ ~ R ~ R ~i o~ ~ ~ ~t ~ ~ ~ ~ ~ ~
CJO _ , __ _ _ _ ~2L
I P~ 00 ~ CO O ~ ~ O OD O~ aD O ~ O ~ Ul ~ ~.~ _ æ O O O _ O æ ___ ` æ _ O ~ E E E E Ei E3 E ~ E ~3 E3 ~ ~ 4~
-l ~ ~ ~ u~ `o l~ o~ o` -~ -~ -~ ~ ~ ~
~ ~,~
_ 14 --13~
Conclusion As clearly recognized from the foregoing Experimental dsta, significant aggregation or crystal growth was observed and also suspensibility was decreased to about 50% after one month ~t 40C
on the reference formulations which represent the prior arts;
while on the formulations of tbe present invention, no crystal growth nor decrease in suspensibility was observed under tbe ssme conditions as the reference.
Claims
(1) A stable suspension-type pesticide formulation prepared by dispersing fine particles of a hydrophobic solid agrochemical in an aqueous medium, wherein the dispersion is achieved with a surfactant and a water-immisible solvent in which said agrochemical is highly soluble.
(2) A stable suspension-type pesticide formulation claimed in Claim 1, wherein said hydrophobic solid agrochemical has a melting point lower than 100°C.
(3) A stable suspension-type pesticide formulation claimed in Claim 1, wherein said agrochemical is 3,5-diiodo-4-octanoyloxy-benzonitrile, .alpha.,.alpha.,.alpha.-trifluoro-2,6-dinitro-N,N-dipropyl-para-toluidine, N-butyl-N-ethyl-.alpha.,.alpha.,.alpha.-trifluoro-2,6-dinitro-para-toluidine, 3-diethoxyphosphorylthiomethyl-6-chlorobenzoxazolone or methyl isothiocyanate.
(4) A stable suspension-type pesticide formulation claimed in Claim 1, wherein said water-immisible solvent is employed at a rate of 20 to 200 % by weight, more preferably of 30 to 120 % by weight, to said agrochemical.
(5) A stable suspension-type pesticide formulation claimed in Claim 1, wherein said water-immisible solvent is of a hydrocarbon, halogeno-hydrocarbon, aromatic hydrocarbon having a nitrogen atom, C6 - C12 alkanol, ether, ketone, ester, or fatty acid.
(6) A stable suspension-type pesticide formulation claimed in
Claim 1, wherein said water-immisible solvent is dichloromethane, acetophenone, isophorone, n-octyl alcohol, benzene, toluene, or xylene.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP169254/1986 | 1986-07-17 | ||
| JP61169254A JP2579755B2 (en) | 1986-07-17 | 1986-07-17 | New suspension pesticide formulation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1304593C true CA1304593C (en) | 1992-07-07 |
Family
ID=15883099
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000542020A Expired - Fee Related CA1304593C (en) | 1986-06-17 | 1987-07-14 | Suspension-type pesticide formulation |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0253682A3 (en) |
| JP (1) | JP2579755B2 (en) |
| KR (1) | KR950006918B1 (en) |
| CN (1) | CN87104900A (en) |
| AU (1) | AU612584B2 (en) |
| BR (1) | BR8703717A (en) |
| CA (1) | CA1304593C (en) |
| HU (1) | HUT43916A (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0676281B2 (en) * | 1986-01-17 | 1994-09-28 | 住友化学工業株式会社 | Stabilized oil-in-water pesticide composition |
| GB8906234D0 (en) | 1989-03-17 | 1989-05-04 | Albright & Wilson | Agrochemical suspensions |
| JPH02259002A (en) * | 1989-03-31 | 1990-10-19 | Showa Electric Wire & Cable Co Ltd | Manufacture of copper flake for brake material |
| KR0153265B1 (en) * | 1989-04-07 | 1998-10-15 | 가와노 다께히꼬 | Isothiocyanate vapor generating agent, germ destroying treatment method using isothiocyanate vapors and apparatus therefor |
| US5078781A (en) * | 1989-06-30 | 1992-01-07 | Imperial Chemical Industries Plc | Bipyridilium herbicidal compositions |
| AU6635990A (en) * | 1989-11-09 | 1991-06-13 | Minato Company Ltd. | Process involving sterilization step, product having bacteriocidal activity and process for preparing the same, fumigant, fumigation method, and bacteriocidal gas composition, and process and apparatus for preparing the same |
| US7332457B2 (en) | 2000-09-18 | 2008-02-19 | Honeywell International Inc. | Agricultural chemical suspensions |
| FR2814089B1 (en) * | 2000-09-21 | 2003-07-04 | Ethypharm Lab Prod Ethiques | PROCESS FOR ISOLATING AND DRYING MICROPARTICLES (MICROSPHERES OR MICROCAPSULES) INITIALLY DISPERSED OR SUSPENDED IN THE LIQUID PHASE |
| WO2002082900A1 (en) * | 2001-03-30 | 2002-10-24 | Rhodia Inc. | Aqeuous suspension of nanoparticles comprising an agrochemical active ingredient |
| JP5235255B2 (en) * | 2001-07-19 | 2013-07-10 | クミアイ化学工業株式会社 | Seed disinfection method |
| FR2870673B1 (en) * | 2004-05-28 | 2006-07-14 | Rhodia Chimie Sa | SOLID FORMULATION COMPRISING A PHYTOSANITARY PRODUCT |
| BRPI1105523A2 (en) | 2011-12-12 | 2013-11-12 | Oxiteno Sa Ind E Comercio | THICKENING COMPOSITION FOR USE IN AGRICULTURAL FORMULATIONS, USE OF A THICKNESS COMPOSITION, AND AGRICULTURAL FORMULATIONS CONTAINING THICKNESS COMPOSITION |
| CN108289452A (en) | 2015-11-30 | 2018-07-17 | 组合化学工业株式会社 | Aqueous suspension composition pesticide and its distributing method |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS526343B2 (en) * | 1971-11-16 | 1977-02-21 | ||
| JPS4887031A (en) * | 1972-02-23 | 1973-11-16 | ||
| FR2197516A1 (en) * | 1972-09-01 | 1974-03-29 | Sandoz Sa | Stable colloidal biocidal formulations - prepd by emulsifying liq. components before adding others including active components esp. herbicides, pesticides, then milling |
| JPS5238094A (en) * | 1975-09-19 | 1977-03-24 | Tadashi Arai | Method of producing antibiotics, mimosamycin and chlorocarcin a, b, c |
| CA1142850A (en) * | 1979-03-26 | 1983-03-15 | George W. Gaertner | Pesticidally-active concentrated oil-in- water emulsions |
| JPS58124702A (en) * | 1982-01-21 | 1983-07-25 | Kumiai Chem Ind Co Ltd | Aqueous suspension of agricultural chemical composition |
| DE3302648A1 (en) * | 1983-01-27 | 1984-08-02 | Hoechst Ag, 6230 Frankfurt | PLANT PROTECTION AGENT IN THE FORM OF MIXED DISPERSIONS |
| JPS61126001A (en) * | 1984-11-22 | 1986-06-13 | Kao Corp | Aqueous suspension of biocide composition, and production thereof |
| JPH0676281B2 (en) * | 1986-01-17 | 1994-09-28 | 住友化学工業株式会社 | Stabilized oil-in-water pesticide composition |
-
1986
- 1986-07-17 JP JP61169254A patent/JP2579755B2/en not_active Expired - Fee Related
-
1987
- 1987-07-14 CA CA000542020A patent/CA1304593C/en not_active Expired - Fee Related
- 1987-07-16 KR KR1019870007771A patent/KR950006918B1/en active IP Right Grant
- 1987-07-16 HU HU873257A patent/HUT43916A/en unknown
- 1987-07-16 BR BR8703717A patent/BR8703717A/en active Search and Examination
- 1987-07-17 CN CN198787104900A patent/CN87104900A/en active Pending
- 1987-07-17 EP EP19870306380 patent/EP0253682A3/en not_active Withdrawn
- 1987-07-17 AU AU75778/87A patent/AU612584B2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| KR880001208A (en) | 1988-04-22 |
| CN87104900A (en) | 1988-01-27 |
| AU612584B2 (en) | 1991-07-18 |
| EP0253682A3 (en) | 1990-09-26 |
| JP2579755B2 (en) | 1997-02-12 |
| HUT43916A (en) | 1988-01-28 |
| KR950006918B1 (en) | 1995-06-26 |
| BR8703717A (en) | 1988-03-29 |
| AU7577887A (en) | 1988-01-21 |
| EP0253682A2 (en) | 1988-01-20 |
| JPS6327401A (en) | 1988-02-05 |
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